JPH08283396A - Crystalline copolymer of p-dioxanone with glycolide - Google Patents

Crystalline copolymer of p-dioxanone with glycolide

Info

Publication number
JPH08283396A
JPH08283396A JP8035707A JP3570796A JPH08283396A JP H08283396 A JPH08283396 A JP H08283396A JP 8035707 A JP8035707 A JP 8035707A JP 3570796 A JP3570796 A JP 3570796A JP H08283396 A JPH08283396 A JP H08283396A
Authority
JP
Japan
Prior art keywords
dioxanone
glycolide
temperature
hours
polymer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
JP8035707A
Other languages
Japanese (ja)
Other versions
JP2713397B2 (en
Inventor
Rao S Bezwada
ラオ・スリニバサ・ベズワダ
Shalaby W Shalaby
シヤラビイ・ウオーバ・シヤラビイ
Jr Hugh D Newman
ヒユー・デイ・ニユーマン・ジユニア
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ethicon Inc
Original Assignee
Ethicon Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ethicon Inc filed Critical Ethicon Inc
Publication of JPH08283396A publication Critical patent/JPH08283396A/en
Application granted granted Critical
Publication of JP2713397B2 publication Critical patent/JP2713397B2/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/66—Polyesters containing oxygen in the form of ether groups
    • C08G63/664—Polyesters containing oxygen in the form of ether groups derived from hydroxy carboxylic acids
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L17/00—Materials for surgical sutures or for ligaturing blood vessels ; Materials for prostheses or catheters
    • A61L17/06—At least partially resorbable materials
    • A61L17/10—At least partially resorbable materials containing macromolecular materials
    • A61L17/12—Homopolymers or copolymers of glycolic acid or lactic acid
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S525/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S525/937—Utility as body contact e.g. implant, contact lens or I.U.D.

Abstract

PROBLEM TO BE SOLVED: To obtain crystalline copolymers of p-dioxanone with glycolide having good flexibility and quick absorbing capacity.
SOLUTION: Desired crystalline copolymers of p-dioxanone with glycolide have about 3 - about 30 wt.% polymerized glycolide and the balance of a polymerized p-dioxanone and, simultaneously, an inherent viscosity of 1.6-2.6 dl/g; a melting temperature, measured by a heated stage microscope, of 90-125°C; a degree of crystallinity of 20-50%; a single molecular weight distribution curve; and a single phase in melt state.
COPYRIGHT: (C)1996,JPO

Description

【発明の詳細な説明】Detailed Description of the Invention

【０００１】本発明はp−ジオキサノンとグリコリドの
結晶性共重合体、該共重合体の製造方法、及びそれから
製造した、たとえば高いコンプライアンス、迅速吸収性
モノフイラメント縫合糸のような手術用品に関するもの
である。The present invention relates to a crystalline copolymer of p-dioxanone and glycolide, a process for producing the copolymer and surgical articles produced therefrom, such as high compliance, rapid absorbable monofilament sutures. is there.

【０００２】発明の背景 p−ジオキサノンホモポリマーから成る、手術用品、特
に吸収性モノフイラメント縫合糸、及び結紮具及び止血
結紮クリツプは有用な商品である。本発明はホモポリマ
ーにおいて達成することができるものとは異なった性質
を有するp−ジオキサノン重合体を提供するための手段
を目的としている。すなわち本発明はp−ジオキサノン
重合体の有用性を拡大するための手段を提供する。[0002] consisting of background p--dioxanone polymers of the invention, surgical items, particularly absorbent monofilament sutures and ligatures and hemostatic ligating clips are useful products. The present invention is directed to a means for providing p-dioxanone polymers that have different properties than can be achieved in homopolymers. That is, the present invention provides a means for extending the usefulness of p-dioxanone polymers.

【０００３】p−ジオキサノン重合体は米国特許第４,０
５２,９８８号においてドツジらによって開示されてい
るが、かれらは、このような重合体から成る縫合糸及び
その他の手術用品をも開示し且つ特許請求している。ド
ツジらの特許の８及び９縦行にわたる記事中で、グリコ
リドをp−ジオキサノンと共重合させて吸収性の縫合糸
を与えることができるということを開示している。P-dioxanone polymers are described in US Pat.
No. 52,988, by Dotuji et al., Which also discloses and claims sutures and other surgical articles made from such polymers. In the 8 and 9 vertical articles of the Dotsuji et al. Patent, it is disclosed that glycolide can be copolymerized with p-dioxanone to provide absorbable sutures.

【０００４】p−ジオキサノンホモポリマーの縫合糸及
び結紮具のような手術用フイラメントは、モノフイラメ
ントの形態で商業的に入手することができる。モノフイ
ラメント縫合糸の望ましい性質の一つは、高い強度(引
張強さと結節強さとして)及び良好なコンプライアンス
又は柔軟性を兼ね備えていることである。p−ジオキサ
ノンホモポリマーの手術用フイラメントは、どちらかと
いえば、こわく且つ針金のようであると外科医によって
認められている。本発明の価値ある利点の一つは、本発
明がp−ジオキサノンホモポリマーよりも柔軟性であるp
−ジオキサノン重合体を提供し、それによってp−ジオ
キサノン重合体の有用性を実質的に増進することであ
る。Surgical filaments such as p-dioxanone homopolymer sutures and ligatures are commercially available in the form of monofilaments. One of the desirable properties of monofilament sutures is their combination of high strength (as tensile and knot strength) and good compliance or flexibility. Surgical filaments of p-dioxanone homopolymer have been found by surgeons to be rather stiff and wire-like. One of the valuable advantages of the present invention is that it is more flexible than p-dioxanone homopolymers.
To provide a dioxanone polymer, thereby substantially enhancing the usefulness of the p-dioxanone polymer.

【０００５】本発明の要約 本発明の重合体は、ポリ(p−ジオキサノン)よりも遥か
に良好な柔軟性と共に高グリコリド重合体の迅速吸収性
を兼ね備えている、p−ジオキサノンとグリコリドの結
晶性共重合体である。さらに本発明は、これらの共重合
体から成る、殺菌できる手術用品、好ましくは良好な強
度、迅速吸収性及びすぐれた柔軟性(低ヤング率によっ
て表わされる)の望ましい組合わせを有するモノフイラ
メント縫合糸及び結紮具をも提供する。本発明によって
提供されるその他の有用な手術用品は、手術用ステープ
ル、たとえば神経及び小脈管吻合のための小直径鞘のよ
うな管状構造物、及び織成又は不織管状構造物を含む織
物を包含する。SUMMARY OF THE INVENTION The polymers of the present invention combine p-dioxanone and glycolide crystallinity with much better flexibility than poly (p-dioxanone) and the rapid absorption of high glycolide polymers. It is a copolymer. The present invention further provides a sterilizable surgical article comprising these copolymers, preferably a monofilament suture having the desired combination of good strength, rapid absorbency and excellent flexibility (represented by a low Young's modulus). And a ligature is also provided. Other useful surgical articles provided by the present invention include surgical staples, tubular structures such as small diameter sheaths for nerve and small vessel anastomosis, and fabrics including woven or non-woven tubular structures. Includes.

【０００６】さらに本発明は：p−ジオキサノンホモポ
リマーとp−ジオキサノンモノマーの混合物にグリコリ
ドを添加し且つそれによって得た反応混合物をp−ジオ
キサノンとグリコリドの共重合体を生じさせるために十
分な時間にわたって高い温度にさらすことから成る本発
明の共重合体の製造方法をも提供する。The present invention further provides: to add glycolide to a mixture of p-dioxanone homopolymer and p-dioxanone monomer and to thereby form the reaction mixture to form a copolymer of p-dioxanone and glycolide. Also provided is a method of making the copolymer of the present invention, which comprises exposing to elevated temperature for a sufficient period of time.

【０００７】従来の技術 前記のドツジらの特許(これは本申請者によって、もつ
とも関連する従来技術と考えられる)に加えて、モノマ
ーの連続的添加による吸収性重合体の製造を開示してい
るという点で、その他の多くの特許が本発明と関連して
いる。これらの特許は、オクズミら、米国特許第４,１
３７,９２１号及び４,１５７,４３７号及びローゼンス
アフトら、米国特許第４,２４３,７７５号及び４,３０
０,５６５号を包含する。PRIOR ART In addition to the above-cited Dotsuji et al. Patent, which is believed by the applicant to be the prior art to which it relates, it discloses the preparation of absorbent polymers by the continuous addition of monomers. In that regard, many other patents are associated with the present invention. These patents are referred to by Okuzumi et al., US Pat.
37,921 and 4,157,437 and Rosens Aft et al., U.S. Pat. Nos. 4,243,775 and 4,30.
0,565 is included.

【０００８】本発明の詳細な記述 本発明の方法を遂行するためのもつとも便宜的な方策
は、先ずp−ジオキサノンモノマーの溶融重合を行なっ
てポリ(p−ジオキサノン)ホモポリマーとp−ジオキサノ
ンモノマーの混合物を生じさせ、次いでこの混合物をグ
リコリドとの反応に使用することである。この単独重合
は、たとえばオクタン酸すずのような適当な金属含有触
媒の触媒として有効な量の存在において行なわれる。触
媒の典型的な割合は、約１０,０００：１乃至約６０,０
００：１、好ましくは約１,５０００：１乃至約４０,０
００：１のモノマー：触媒モル比において認められる。
重合は、たとえばアルカノール、グリコール、ヒドロキ
シ酸又はアミンのような開始剤の存在においあて行なわ
れる。このような開始剤の特定的な例は、１ードデカノ
ール、ジエチレングリコール、グリコール酸、乳酸、エ
タノールアミンなどを包含する。開始剤の典型的な割合
は、約５００：１乃至約１８００：１のモノマー：開始
剤モル比において認められる。p−ジオキサノンの重合
は、不活性雰囲気下に高い温度において、p−ジオキサ
ノンホモポリマーとp−ジオキサノンのモノマーの混合
物を生じさせるために十分な時間にわたって、行なわれ
る。典型的な重合反応温度は約１００℃乃至約１３０℃
の範囲内であり、約１１０℃が好ましい。重合反応は重
合体とモノマーの間で平衡に達するまで行なわれる。こ
の平衡は通常は、モノマーとポリマーの合計重量に基づ
いて、約１５〜３０重量パーセントのモノマーにおいて
得られる。温度に依存して、この反応は通常は約４〜約
８時間を要する。約１１０℃の好適温度では、通常の反
応時間は５〜６時間である。DETAILED DESCRIPTION OF THE INVENTION A convenient and expedient way to carry out the process of the present invention is to first perform a melt polymerization of p-dioxanone monomers to form poly (p-dioxanone) homopolymer and p-dioxanone. To produce a mixture of oxanone monomers, which is then used in the reaction with glycolide. This homopolymerization is carried out in the presence of a catalytically effective amount of a suitable metal-containing catalyst such as tin octoate. Typical proportions of catalyst are from about 10,000: 1 to about 60,0.
00: 1, preferably about 15,000: 1 to about 40,0
Permitted at a monomer: catalyst molar ratio of 00: 1.
The polymerization is carried out in the presence of initiators such as alkanols, glycols, hydroxy acids or amines. Specific examples of such initiators include 1-dodecanol, diethylene glycol, glycolic acid, lactic acid, ethanolamine and the like. Typical ratios of initiators are found in monomer: initiator molar ratios of about 500: 1 to about 1800: 1. Polymerization of p-dioxanone is carried out at elevated temperature under an inert atmosphere for a time sufficient to form a mixture of p-dioxanone homopolymer and p-dioxanone monomer. Typical polymerization reaction temperatures range from about 100 ° C to about 130 ° C.
Of about 110 ° C. is preferred. The polymerization reaction is carried out until equilibrium is reached between the polymer and the monomer. This equilibrium is typically obtained at about 15-30 weight percent monomer, based on the total weight of monomer and polymer. Depending on the temperature, this reaction usually requires about 4 to about 8 hours. At the preferred temperature of about 110 ° C., typical reaction times are 5-6 hours.

【０００９】次の段階はp−ジオキサノンのホモポリマ
ーとモノマーの混合物にグリコリドを添加し、且つそれ
によって得た反応混合物を本発明のセグメント共重合体
を生じさせるために十分な時間にわたって高い温度にさ
らすことである。原則として、この重合に対する反応温
度は約１２０℃乃至約１８０℃の範囲内であり、且つ１
２０〜１５０℃が好ましい。この範囲内の反応温度にお
いて、重合は約１乃至約４時間以内に完了する。The next step is to add glycolide to the mixture of p-dioxanone homopolymer and monomer, and to heat the resulting reaction mixture to an elevated temperature for a time sufficient to form the segmented copolymers of this invention. To expose. In principle, the reaction temperature for this polymerization is in the range of about 120 ° C to about 180 ° C, and 1
20-150 degreeC is preferable. At reaction temperatures within this range, polymerization is complete within about 1 to about 4 hours.

【００１０】p−ジオキサノンホモポリマーとモノマー
の混合物に加えるグリコリドの割合は通常は、反応混合
物の全重量(すなわち、グリコリド、p−ジオキサノンホ
モポリマー及びp−ジオキサノンモノマーの合計重量)に
基づいて、約３乃至約２５重量パーセント、好ましくは
約５乃至約２０重量パーセントである。The proportion of glycolide added to the mixture of p-dioxanone homopolymer and monomer is usually based on the total weight of the reaction mixture (ie the total weight of glycolide, p-dioxanone homopolymer and p-dioxanone monomer). Based on about 3 to about 25 weight percent, preferably about 5 to about 20 weight percent.

【００１１】以下の実施例は本発明の共重合体の製造を
例証するものである。The following examples illustrate the preparation of the copolymers of this invention.

【００１２】実施例１９５／５初期重量組成(モル％で９５．６／４．４)にお
けるポリジオキサノン溶融物／グリコリドの製造 炎で乾燥させた２５０ｍｌの丸底二つ口フラスコに、窒
素下に９５g(０．９３０６モル)のp−ジオキサノン、
０．２６６ｍｌの１ードデカノール及び０．０９８４ｍ
ｌのオクタン酸すず(トルエン中の０．３３モル濃度溶
液)を入れた。反応フラスコの内容物を室温で高真空下
に約１６時間保った。フラスコに炎で乾燥させた機械的
撹拌機及びホース接続をもつアダプターを付した。反応
器を窒素で３回パージしたのち窒素と共に排気した。反
応混合物を１１０℃に加熱して５時間保った。この重合
体の試料を取出し(インヘレント粘度＝１．２１ｄｌ／
ｇ)、５g(０．０４３０８モル)のグリコリドを加えた。
次いで１５分間かけて温度を１４０℃まで上げ、その温
度で１時間保った。油浴の温度を９０℃に下げ、その温
度で約６５時間保った。重合体を単離し、摩砕したの
ち、８０℃／０．１mmＨgで４８時間乾燥して、未反応
モノマーを除去した。１３．７％の重量減が認められ
た。生成した重合体は熱載物台顕微鏡法による９６〜１
００℃の融点範囲と１．６３ｄｌ／ｇのインヘレント粘
度(“ＩＶ")を有していた。他のことわりがない限り
は、本明細書中に記したすべてのインヘレント粘度は、
２５℃でヘキサフルオロイソプロピルアルコール中の
０．１ｇ／ｄｌの濃度において測定した。Example 1 A 95/5 initial weight composition (95.6 / 4.4 in mol%) was used.
Preparation of Polydioxanone Melt / Glycolide In a flame dried 250 ml round bottom two neck flask, under nitrogen, 95 g (0.9306 mol) of p-dioxanone,
0.266 ml of 1-dodecanol and 0.0984 m
1 of tin octanoate (0.33 molar solution in toluene) was added. The contents of the reaction flask were kept at room temperature under high vacuum for about 16 hours. The flask was equipped with a flame dried mechanical stirrer and an adapter with a hose connection. The reactor was purged with nitrogen three times and then evacuated with nitrogen. The reaction mixture was heated to 110 ° C. and held for 5 hours. A sample of this polymer was removed (inherent viscosity = 1.21 dl /
g), 5 g (0.04308 mol) of glycolide was added.
The temperature was then raised to 140 ° C. over 15 minutes and kept at that temperature for 1 hour. The temperature of the oil bath was lowered to 90 ° C and kept at that temperature for about 65 hours. The polymer was isolated, ground, and dried at 80 ° C./0.1 mmHg for 48 hours to remove unreacted monomers. A weight loss of 13.7% was observed. The resulting polymer was 96-1 by thermal stage microscopy.
It had a melting point range of 00 ° C. and an inherent viscosity (“IV”) of 1.63 dl / g. Unless otherwise stated, all inherent viscosities noted herein are:
It was measured at a concentration of 0.1 g / dl in hexafluoroisopropyl alcohol at 25 ° C.

【００１３】実施例２９０／１０初期重量組成(モル％で９１／９)におけるポ
リジオキサノン−溶融物／グリコリドの製造 炎で乾燥した２５０ｍｌの丸底二つ口フラスコに、窒素
下に９０g(０．８８１６モル)のp−ジオキサノン、０．
２６ｍｌの１ードデカノール及び０．０９８ｍｌのオク
タン酸すず(トルエン中０．３３モル濃度溶液)を入れ
た。反応フラスコの内容物を室温において高真空下に約
１６時間保った。フラスコに炎で乾燥した機械的撹拌機
とホース連結をもつアダプターを付した。反応混合物を
窒素流下に１１０℃に加熱して、その温度で５時間保っ
た。この重合体の試料を取出して、１０g(０．０８６２
モル)のグリコリドを加えた。温度を続く１０分にわた
って１６０℃に上げ、そのまま１時間保った。油浴の温
度を８５℃に下げ、そのまま約６５時間保った。重合物
を単離し、摩砕したのち、８０℃／０．１mmＨgで４８
時間乾燥して、未反応のモノマーを除いた。１３．８％
の重量減が認められた。かくして得た重合物は１００〜
１０５℃の融点範囲（熱載物台顕微鏡法による）、２５
℃において１．４４ｄｌ／ｇのインヘレント粘度、−８
℃のＴg(ＤＳＣによる)、９７℃のＴm(ＤＳＣによる)、
４５％の結晶化度(Ｘ線回折による)及びＮＭＲにより８
７．３／１２．７のＰＤＯ／ＰＧモル比を有していた。
(ＰＤＯ／ＰＧモル比は重合体中の重合したp−ジオキサ
ノンの共重合したグリコリドに対する比であり、１モル
のグリコリドは２グリコール酸単位を含有する)。Example 2 The porosity at 90/10 initial weight composition (91/9 in mol%)
Preparation of Lydioxanone-Melt / Glycolide In a flame dried 250 ml round bottom two neck flask, 90 g (0.8816 mol) of p-dioxanone, 0.
26 ml of 1-dodecanol and 0.098 ml of tin octoate (0.33 molar solution in toluene) were added. The contents of the reaction flask were kept at room temperature under high vacuum for about 16 hours. The flask was equipped with a flame dried mechanical stirrer and an adapter with a hose connection. The reaction mixture was heated to 110 ° C. under a stream of nitrogen and kept at that temperature for 5 hours. A sample of this polymer was removed and 10 g (0.0862)
Mol) glycolide was added. The temperature was raised to 160 ° C over the next 10 minutes and held there for 1 hour. The temperature of the oil bath was lowered to 85 ° C. and kept as it was for about 65 hours. The polymer was isolated and ground, and then 48 at 80 ° C / 0.1 mmHg.
After drying for an hour, unreacted monomer was removed. 13.8%
The weight loss was confirmed. The polymer thus obtained is 100-
105 ° C melting point range (by thermal stage microscopy), 25
Inherent viscosity of 1.44 dl / g at -8, -8
℃ Tg (by DSC), Tm 97 ℃ (by DSC),
45% crystallinity (by X-ray diffraction) and 8 by NMR
It had a PDO / PG molar ratio of 7.3 / 12.7.
(The PDO / PG molar ratio is the ratio of polymerized p-dioxanone to copolymerized glycolide in the polymer, 1 mole of glycolide containing 2 glycolic acid units).

【００１４】実施例３８０／２０初期重量組成(モル％で８２／１８)における
ポリジオキサノン−溶融物／グリコリドの製造 炎で乾燥した、２５０ｍｌの丸底２つ口フラスコに、窒
素下に８０g(０．７８３６モル)のp−ジオキサノン、
０．２１７ｍｌの１ードデカノール及び０．０４８ｍｌ
のオクタン酸すず(トルエン中０．３３モル濃度溶液)を
入れた。反応フラスコの内容物を窒素下に室温で約１６
時間保った。フラスコに炎で乾燥した機械的撹拌機とホ
ース接続をもつアダプターを付した。反応混合物を窒素
流下に１１０℃に加熱し、その温度で５時間保った。こ
の重合物の試料を取出して、２０g(０．１７２３モル)
のグリコリドを加えた。温度を１４０℃に上げて、その
温度に１時間保った。油浴の温度を続く１０分間にわた
って１６０℃に上げ、その温度で約４０分保った。重合
体を単離し、摩砕し且つ８０℃／０．１mmＨgで４８時
間乾燥して、未反応のモノマーを除いた。６．４％の重
量減が認められた。かくして得た重合体は９５〜１００
℃の熱載物台顕微鏡法による溶融範囲、１．６４ｄｌ／
ｇのインヘレント粘度及び４０％の結晶化度を有してい
た。ＤＳＣによるＴgは−２℃であり、Ｔmは１２５℃で
あったが、１９３℃における第二のＴmが示唆された。
ＰＤＯ／ＰＧモル比はＮＭＲによって８２．７／１７．
３であることが認められた。Example 3 80/20 in initial weight composition (82/18 in mol%)
Preparation of Polydioxanone-Melt / Glycolide In a flame dried, 250 ml round bottom two neck flask, 80 g (0.7836 mol) of p-dioxanone under nitrogen,
0.217 ml of 1-dodecanol and 0.048 ml
Stannous octoate (0.33 molar solution in toluene) was added. The contents of the reaction flask were placed under nitrogen at room temperature to about 16
I kept it for hours. The flask was equipped with a flame-dried mechanical stirrer and an adapter with a hose connection. The reaction mixture was heated to 110 ° C. under a stream of nitrogen and kept at that temperature for 5 hours. 20 g (0.1723 mol) of a sample of this polymer was taken out.
Of glycolide was added. The temperature was raised to 140 ° C. and kept there for 1 hour. The temperature of the oil bath was raised to 160 ° C. over the next 10 minutes and kept at that temperature for about 40 minutes. The polymer was isolated, ground and dried at 80 ° C./0.1 mm Hg for 48 hours to remove unreacted monomer. A weight loss of 6.4% was observed. The polymer thus obtained is 95-100.
Melting range by thermal stage microscopy at 1.degree. C., 1.64 dl /
It had an inherent viscosity of g and a crystallinity of 40%. The DSC Tg was -2 ° C and the Tm was 125 ° C, suggesting a second Tm at 193 ° C.
The PDO / PG molar ratio is 82.7 / 17.
It was recognized that it was 3.

【００１５】押出し 繊維、特に手術用フイラメントの製造において、共重合
体を常法に従って下記の一般的手順により紡糸口金を通
じて溶融押出しして、１本以上のフイラメントを形成さ
せた。In the manufacture of extruded fibers, especially surgical filaments, the copolymer was melt extruded through a spinneret according to the following general procedure according to conventional methods to form one or more filaments.

【００１６】ここに記した共重合体の押出しは、インス
トロン毛細管レオメーターを用いて行なった。共重合体
を予熱(８０〜９０℃)した押出室中に充てんして、２cm
／分のラム速度と押出し温度における９〜１２分の滞留
時間後に、４０ミルのダイ(Ｌ／Ｄ＝２４．１)を通じて
押出した。押出し温度は重合体のＴmと与えられた温度
における材料の溶融粘度に依存するけれども、Ｔmより
も約１０〜７５℃高い温度における当該共重合体の押出
しが、一般に好都合である。実施例に記した共重合体の
押出し温度は１２０〜２０５℃の範囲であった。押出物
は通常は、氷水の急冷浴を通じて２４フイート／分で引
き取ったけれども、場合によっては、異なる浴温と引き
取り速度を使用した。インストロン毛細管レオメータの
代りにスクリユー形押出機又は類似の装置を用いること
もできる。Extrusion of the copolymers described herein was carried out using an Instron capillary rheometer. Fill the preheated (80-90 ° C) extrusion chamber with the copolymer and
Extrusion through a 40 mil die (L / D = 24.1) after a ram speed of / min and a residence time of 9-12 minutes at extrusion temperature. Although the extrusion temperature depends on the Tm of the polymer and the melt viscosity of the material at a given temperature, extrusion of the copolymer at a temperature about 10 to 75 ° C above the Tm is generally convenient. The extrusion temperatures of the copolymers described in the examples were in the range 120-205 ° C. The extrudates were typically drawn through a quench bath of ice water at 24 ft / min, but in some cases different bath temperatures and draw rates were used. Instead of an Instron capillary rheometer, a screw extruder or similar device can be used.

【００１７】押出したフイラメントを次いで、分子配向
を与えて引張特性を向上させるために、１段又は多段延
伸法により約６×乃至７×延伸する。延伸は次のように
して行なう：押出物(直径範囲１６〜２０ミル)を４フイ
ート／分の入力速度でローラーを通じてグリセリンの加
熱延伸浴中に通じる。延伸浴の温度は約２５〜９０℃の
範囲で変えることができるが、本明細書中の実施例では
４９〜５８℃の温度を用いる。この延伸の第一段階にお
ける延伸比は３×乃至約７×の範囲で変えることができ
るが、記載の実施例では４×乃至５．５×の第一段延伸
比を用いる。部分的に延伸した繊維を次いで第二の組の
ローラー上で５０〜９５℃の範囲の温度に保ったグリセ
リン浴(第二段階)中に送るが、記載の実施例においては
７０〜７５℃の第二段延伸温度を用いる。この第二段階
においては２×に至るまでの延伸比を与えるが、実施例
中では１．２×乃至１．６×の範囲の延伸比を用いた。
繊維を水浴を通じてスプール上に巻き取り且つ乾燥す
る。グリセリン延伸浴の一部又は全部の代りに、一組の
熱ローラーを用いることができる。このようにして得た
配向したフイラメントは良好な引張及び結節強さを有し
ている。The extruded filaments are then stretched by about 6 × to 7 × by a single-stage or multi-stage stretching method to impart molecular orientation and improve tensile properties. The drawing is carried out as follows: The extrudate (diameter range 16-20 mils) is passed through a roller into a heated drawing bath of glycerin at an input speed of 4 feet / minute. The temperature of the stretching bath can be varied in the range of about 25-90 ° C, although in the examples herein a temperature of 49-58 ° C is used. The draw ratio in the first stage of this draw can vary from 3 × to about 7 ×, but in the described examples a first stage draw ratio of 4 × to 5.5 × is used. The partially drawn fibers are then sent on a second set of rollers into a glycerin bath (second stage) kept at a temperature in the range of 50-95 ° C, but in the described example at 70-75 ° C. A second draw temperature is used. In this second stage, stretch ratios up to 2x are given, but in the examples stretch ratios in the range 1.2x to 1.6x were used.
The fiber is wound on a spool through a water bath and dried. A set of hot rollers can be used in place of some or all of the glycerin drawing bath. The oriented filaments thus obtained have good tensile and knot strength.

【００１８】配向フイラメントの寸法安定性と生体内引
張強さの保持は、フイラメントに焼きなまし処理を施す
ことによって増進することができる。この任意な処理
は、延伸したフイラメントをフイラメントの実質的な収
縮を防ぐように拘束しながら、約４０〜９０℃、もつと
も好ましくは約６０〜８０℃の温度に加熱することから
成っている。この工程は、最初に張力下にあるフイラメ
ントを用いて、又は拘束前に２０％に至るまでの収縮を
許したフイラメントを用いて、始めることができる。フ
イラメントは、温度及び処理条件に依存して、数秒乃至
数日以上にわたって焼きなまし温度に保つ。一般に６０
〜８０℃において約２４時間に至るまでの焼きなましが
本発明の共重合体に対して適当である。生体内におけ
る、最高の繊維の強度保持と寸法安定性のために最適な
焼きなまし時間及び温度は、各繊維組成物に対して簡単
な実験によって容易に決定することができる。Dimensional stability and retention of tensile strength in vivo of oriented filaments can be enhanced by subjecting the filaments to an annealing treatment. This optional treatment consists of heating the drawn filament to a temperature of about 40-90 ° C, and preferably about 60-80 ° C, while constraining to prevent substantial contraction of the filament. This process can be started with filaments initially under tension or with filaments that allowed up to 20% shrinkage before restraint. The filament is kept at the annealing temperature for a few seconds to a few days or longer, depending on the temperature and processing conditions. Generally 60
Annealing at -80 ° C for up to about 24 hours is suitable for the copolymers of this invention. Optimal annealing times and temperatures for maximum fiber strength retention and dimensional stability in vivo can be readily determined by simple experimentation for each fiber composition.

【００１９】このようにして製造したフイラメントを縫
合糸又は結紮具に加工し、手術針に取り付け、包装し且
つ公知の方法によって滅菌することができる。The filament thus produced can be processed into a suture or a ligature, attached to a surgical needle, packaged and sterilized by known methods.

【００２０】本発明のフイラメントの特性は、通常の試
験方法によって容易に決定することができる。本明細書
中に示した引張特性(すなわち引張強さ、結節強さ、ヤ
ング率、及び伸び)はインストロン引張試験機を用いて
測定した。引張強さ、結節強さ、伸び及びヤング率の測
定のために用いた条件設定は、他のことわりがない限り
は、次のようなものとした: 引張強さは、切断に至る力を繊維の初期断面積で除すこ
とによって計算する。伸びは、１cmの水平移動当り４−
1/6％を割当てる試料の応力−ひずみ曲線から直接に読
みとる。The properties of the filaments of the present invention can be readily determined by conventional test methods. The tensile properties (ie, tensile strength, knot strength, Young's modulus, and elongation) shown herein were measured using an Instron tensile tester. The conditions used for measuring tensile strength, knot strength, elongation and Young's modulus were as follows, unless otherwise stated: Tensile strength is calculated by dividing the force leading to breaking by the initial cross-sectional area of the fiber. Elongation is 4-per 1 cm horizontal movement
Read directly from the stress-strain curve of the sample to which 1 / 6 % is assigned.

【００２１】ヤング率は、試料の応力−ひずみ曲線の直
線的弾性区域の傾斜から、次のようにして計算する：Young's modulus is calculated from the slope of the linear elastic zone of the sample stress-strain curve as follows:

【００２２】[0022]

【数１】 [Equation 1]

【００２３】θは傾斜と水平軸の間の角度であり、ＸＳ
は繊維の初期断面積であり、ＳＬは比例荷重であり、Ｘ
Ｈはクロスヘツド速度であり、ＣＳはチヤート速度であ
り、ＧＬはゲージ長さである。ＳＬはθが４５°に近く
なるように選ぶとよい。Θ is the angle between the tilt and the horizontal axis, XS
Is the initial cross-sectional area of the fiber, SL is the proportional load, X
H is the crosshead speed, CS is the chart speed, and GL is the gauge length. SL should be selected so that θ is close to 45 °.

【００２４】繊維の結節強さは、別個の実験で決定す
る。試験製品を内径1/4インチ、壁厚1/16インチの軟質
管の周囲にフイラメントを１回転させて外科医の結び目
として結ぶ。外科医の結び目は、先ず自由端を輪中に１
回ではなく２回通し、且つ一つの結び目が複合結び目上
に重なるように末端をぴんと伸ばした、四角い結び目で
ある。第一の結び目は、左端を右端上にして開始し且つ
十分な張力を加えて結び目をしっかりと結ぶ。The knot strength of the fibers is determined in a separate experiment. The test product inside diameter 1/4 inches by 1 rotation of the filament around flexible pipe wall thickness 1/16 inch connecting a surgeon's knot. The surgeon's knot is 1 with the free end in the loop.
It is a square knot that is passed twice instead of once, and the ends are stretched so that one knot overlaps the compound knot. The first knot starts with the left end on the right end and applies sufficient tension to tie the knot tight.

【００２５】結び目をクランプのほぼ中間に置いて試験
試料をインストロン引張試験機中に置く。結節強さは切
断に要する力を繊維の初期断面積で除すことによって計
算する。The test sample is placed in the Instron Tensile Tester with the knot approximately midway between the clamps. Knot strength is calculated by dividing the force required to cut by the initial cross-sectional area of the fiber.

【００２６】引張強さ値とヤング率(Ｙ．Ｍ．)をＫＳＰ
Ｉ又はＫＳＰＩ×１０3として記録する。The tensile strength value and the Young's modulus (YM) are calculated as KSP.
Record as I or KSPI × 10 3 .

【００２７】実施例４〜６ 実施例１〜３に記した共重合体をモノフイラメント繊維
として押出した。配向条件を第１表中に示し、これらの
共重合体の引張特性を第２表に示す。Examples 4-6 The copolymers described in Examples 1-3 were extruded as monofilament fibers. The orientation conditions are shown in Table 1 and the tensile properties of these copolymers are shown in Table 2.

【００２８】 第１表 配向条件 共重合体 繊 維 第１段 第２段 全延伸比実施例番号 実施例番号 延 伸 延 伸 1 4 4X 1.562X 6.25X (58℃) (75℃) 2 5 5X 1.3X 6.5X (52℃) (72℃) 3 6 5X 1.2X 6X (50℃) (71℃) 第２表 共重合体 実施例 実施例 実施例 実施例番号 １ ２ ３ 当初PDO/PG 重量比 95/5 90/10 80/20配向繊維の性質 繊維 実施例番号 ４ ５ ６ 引張強さ、ＫＳＰＩ 88 87 65 結節強さ、ＫＳＰＩ 53 49 43 伸び、％ 49 61 94 ヤング率、ＫＳＰＩ 211 143 81 焼きなまし 12hr/60℃(2) 12hr/60℃ 12hr/60℃ 引張強さ、ＫＳＰＩ 79 85 61 結節強さ、ＫＳＰＩ 50 62 51 伸び、％ 34 39 55 ヤング率、ＫＳＰＩ 281 283 201 試験管内BSR(1) 4日/50℃ 79％ 49％ 43％ (１) 指示温度のりん酸塩緩衝液(pＨ＝７．２６)中の指
示日数後の引張強さの当初引張強さに対する保持率 (２) 収縮なし 実施例７開始剤としてジエチレングリコールを使用する９０／１
０初期重量組成(モル％で９１／９)におけるポリジオキ
サノン−溶融物／グリコリドの製造 炎で乾燥した、２５０ｍｌの丸底二つ口フラスコに、窒
素下に９０g(０．８８１６モル)のp−ジオキサノン、
０．０５５ｍｌのジエチレングリコール及び０．０９８
ｍｌのオクタン酸すず(トルエン中０．３３モル溶液)を
入れた。反応フラスコの内容物を室温で約１６時間保っ
た。フラスコに炎で乾燥した機械的撹拌機とホース接続
をもつアダプターを付した。反応混合物を窒素流下に１
１０℃に加熱し、その温度で５時間保った。この重合物
の試料を取出して(インヘレント粘度１．１６ｄｌ／
ｇ)、１０g(０．０８６２モル)のグリコリドを加えた。
温度を次の１０分間で１６０℃まで上げ、そのまま１時
間保った。油浴の温度を８５℃まで下げ、そのまま約６
５時間保った。重合体を単離し、摩砕し且つ８０℃／
０．１mmＨgで４８時間乾燥して、未反応モノマーを除
いた。かくして得た重合体は熱載物台顕微鏡法による９
４〜９９℃の融点範囲と１．８８ｄｌ／ｇのインヘレン
ト粘度を有していた。 Table 1 Orientation Condition Copolymer Fiber 1st Stage 2nd Stage Total Stretch Ratio Example No. Example No. Stretching Stretching 1 4 4X 1.562X 6.25X (58 ° C) (75 ° C) 2 5 5X 1.3X 6.5X (52 ° C) (72 ° C) 3 6 5X 1.2X 6X (50 ° C) (71 ° C) Table 2 Copolymer Example Example Example Example Example No. 1 2 3 Initial PDO / PG weight ratio 95/5 90/10 80/20 Properties of oriented fiber Fiber No. 4 5 6 Tensile strength, KSPI 88 87 65 Knot strength, KSPI 53 49 43 Elongation,% 49 61 94 Young's modulus, KSPI 211 143 81 Annealed 12hr / 60 ℃ (2) 12hr / 60 ℃ 12hr / 60 ℃ Tensile strength, KSPI 79 85 61 Knot strength, KSPI 50 62 51 Elongation,% 34 39 55 Young's modulus, KSPI 281 283 201 In-vitro BSR (1) 4 days / 50 ℃ 79% 49% 43% (1) Retention rate of tensile strength after initial number of days in phosphate buffer solution (pH = 7.26) at indicated temperature with respect to initial tensile strength (2) Shrinkage diethylene glycol as none example 7 initiator Using the 90/1
0 Polydioxy at initial weight composition (91/9 in mol%)
Preparation of Sanon-Melt / Glycolide In a flame dried, 250 ml round bottom two neck flask, 90 g (0.8816 mol) of p-dioxanone, under nitrogen,
0.055 ml diethylene glycol and 0.098
ml tin octoate (0.33 molar solution in toluene) was charged. The contents of the reaction flask were kept at room temperature for about 16 hours. The flask was equipped with a flame-dried mechanical stirrer and an adapter with a hose connection. The reaction mixture was placed under a stream of nitrogen 1
Heat to 10 ° C. and hold at that temperature for 5 hours. A sample of this polymer was taken (inherent viscosity 1.16 dl /
g), 10 g (0.0862 mol) of glycolide was added.
The temperature was raised to 160 ° C over the next 10 minutes and held there for 1 hour. Lower the temperature of the oil bath to 85 ° C and leave it at about 6
I kept it for 5 hours. The polymer is isolated, ground and 80 ° C /
Unreacted monomers were removed by drying at 0.1 mmHg for 48 hours. The polymer thus obtained is 9 by thermal stage microscopy.
It had a melting point range of 4-99 ° C. and an inherent viscosity of 1.88 dl / g.

【００２９】実施例８ 実施例７の共重合体を常法により紡糸口金を通じて押出
した。生じた押出物を２段階で６．５×(５２℃におい
て５×;７２℃において１．３×)延伸したのち、６０℃
で１２時間収縮なしで焼きなましした。焼きなましした
繊維の物理的性質は次のとおりであった: 引張強さ、ＫＳＰＩ ８８ 結節強さ、ＫＳＰＩ ５５ 伸び、％ ３０％ ヤング率、ＫＳＰＩ ２０４ 試験管内ＢＳＲ ４日／５０℃／７.２７pＨ ３４％ 実施例９及び１０９０／１０初期重量組成におけるポリジオキサノン−溶
融物／グリコリドの製造 完全に乾燥した、機械的に撹拌した１．５ガロンのステ
ンレス鋼反応器に１８００g(１７．６３２モル)のp−ジ
オキサノン、３．９６ｍｌの１ードデカノール及び１．
９５５ｍｌのオクタン酸すず(トルエン中０．３３モル
濃度溶液)を仕込んだ。フラスコ内容物を高真空下に室
温で約１６時間保った。反応器を窒素でパージし且つ排
気した。反応混合物を１１０℃に加熱し、そのまま約６
時間保った。重合物の試料を取出して２００g(１．７２
３モル)のグリコリドを加えた。実施例９では温度を１
４０〜１５０℃に上げて約４５分間保ち、一方、実施例
１０においては約１２０℃に上げて約１時間保った。重
合体を単離し、摩砕し且つ乾燥して未反応モノマーを除
いた。これらの実施例の重合物と繊維の性質を第３表に
示す。実施例９の押出し繊維は７×(４９℃で５×、次
いで７２℃で１．４×)延伸し、実施例１０の押出し繊
維は６．７５×(５３℃で５×、７０℃で１．３５×)延
伸した。Example 8 The copolymer of Example 7 was extruded through a spinneret by a conventional method. The resulting extrudate was stretched in two stages at 6.5 × (5 × at 52 ° C .; 1.3 × at 72 ° C.) and then at 60 ° C.
Annealed for 12 hours without shrinkage. The physical properties of the annealed fibers were as follows: Tensile Strength, KSPI 88 Knot Strength, KSPI 55 Elongation,% 30% Young's Modulus, KSPI 204 In Vitro BSR 4 days / 50 ° C / 7.27 pH 34. % Examples 9 and 10 Polydioxanone-soluble at 90/10 initial weight composition
Melt / Glycolide Preparation 1800 g (17.632 mol) of p-dioxanone, 3.96 ml of 1-dodecanol and 1. in a completely dry, mechanically stirred, 1.5 gallon stainless steel reactor.
955 ml of tin octanoate (0.33 molar solution in toluene) were charged. The flask contents were kept under high vacuum at room temperature for about 16 hours. The reactor was purged with nitrogen and evacuated. The reaction mixture was heated to 110 ° C and left to stand for about 6
I kept it for hours. A sample of the polymer was taken out and 200 g (1.72)
3 mol) glycolide was added. In Example 9, the temperature was 1
The temperature was raised to 40 to 150 ° C. and kept for about 45 minutes, while in Example 10, it was raised to about 120 ° C. and kept for about 1 hour. The polymer was isolated, triturated and dried to remove unreacted monomer. The properties of the polymers and fibers of these examples are shown in Table 3. The extruded fiber of Example 9 was drawn 7 × (5 × at 49 ° C., then 1.4 × at 72 ° C.) and the extruded fiber of Example 10 was 6.75 × (5 × at 53 ° C., 1 × at 70 ° C.). .35 ×) stretched.

【００３０】 第３表 ポリジオキサノン−溶融物／グリコリド 実施例９ 実施例10 (自然)(3) (自然)重合体性質 インヘレント粘度、ｄｌ／ｇ 1.77 1.82 融点(熱載物台顕微鏡法) 102℃ 98-102℃繊維性質 配 向 焼きなまし 配 向 焼きなまし 12h/60℃ 12h/60℃ 直径(ミル) 7.8 8.1 7.5 7.8 引張強さ、KSPI 106 89 100 86 結節強さ、KSPI 48 48 51 53 伸び、％ 60 30 63 48 ヤング率、KSPI 134 192 121 221 試験管内BSR(4) 4日/50℃ − 57％ − 55％ 7日/50℃ − − − − 生体内BSR(5) ３週 − 28％ − 30％ ４週 − 17％ − 12％ 生体内吸収(6) ９１日 − 21％ − 23％ １１９日 − 0 − 0 １５４日 − 0 − 0 (３) “自然"は未染色を意味する。 Table 3 Polydioxanone-Melt / Glycolide Example 9 Example 10 (Natural) (3) (Natural) Polymer Properties Inherent Viscosity, dl / g 1.77 1.82 Melting Point (Hot Table Microscopy) 102 ° C 98 -102 ℃ Fiber Properties Directional Annealing Directional Annealing 12h / 60 ℃ 12h / 60 ℃ Diameter (mill) 7.8 8.1 7.5 7.8 Tensile strength, KSPI 106 89 100 86 Knot strength, KSPI 48 48 51 53 Elongation,% 60 30 63 48 Young's modulus, KSPI 134 192 121 221 In vitro BSR (4) 4 days / 50 ° C − 57% − 55% 7 days / 50 ° C − − − − In vivo BSR (5) 3 weeks − 28% − 30% 4 weeks −17% −12% Biosorption (6) 91 days −21% −23% 119 days −0 −0 154 days −0 −0 (3) “Natural” means unstained.

【００３１】(４) 試験管内ＢＳＲ−５０℃のりん酸塩
緩衝液pＨ７.２６中で指示の日数後に残留する引張強さ
の初期引張強さに対する百分率。(4) Percentage of tensile strength remaining after the indicated days in phosphate buffer pH 7.26 at BSR-50 ° C. in vitro, relative to initial tensile strength.

【００３２】(５),(６) 生体内ＢＳＲ及び吸収試験方
法は以下に記すとおりである。(5), (6) In vivo BSR and absorption test method are as described below.

【００３３】生体内引張強さ保持率 繊維の生体内引張強さ保持率(ＢＳＲ)は、多数のロング
−エバンス ラツトの背側の皮下組織中に２本の繊維を
移植することによって測定する。使用するラツトの数は
移植期間に関係し、１期間当り４匹のラツトを使用する
から、各期間に対して全体で８実施例が与えられる。す
なわち、２,３又は４移植周期に相応して各繊維の１６,
２４又は３２本の断片を移植する。生体内滞留の期間
は、７,１４,２１又は２８日である。各期間における引
張強さ(下記条件設定を用いるインストロン引張試験機
によって測定:ゲージ長さ１インチ、チヤート速度１イ
ンチ、クロスヘツド速度１インチ)の８測定の平均値の
移植前の繊維に対して得た平均値(８測定に対して)に対
する比を、各期間に対する引張強さ保持率とする。In- vivo Tensile Strength Retention In- vivo Tensile Strength Retention (BSR) is measured by implanting two fibers in the dorsal subcutaneous tissue of a number of Long-Evans rats. Since the number of rats used is related to the implantation period and 4 rats are used per period, a total of 8 examples are given for each period. Ie 16 of each fiber, corresponding to 2, 3 or 4 implantation cycles,
Transplant 24 or 32 fragments. The period of in-vivo retention is 7, 14, 21 or 28 days. The average value of 8 measurements of tensile strength (measured by an Instron tensile tester using the following condition settings: gauge length 1 inch, chart speed 1 inch, crosshead speed 1 inch) for each fiber before transplantation in each period The ratio to the average value (for 8 measurements) obtained is taken as the tensile strength retention rate for each period.

【００３４】生体内吸収 生体内吸収試験は次のようにして行なう：試料フイラメ
ントの２cmの部分を試験の各期間に対して２匹のめすラ
ツトの左右の両方の臀部筋肉中に移植する。この手順は
５,９１,１１９,１５４及び２１０日の期間に対して各
期間当り全体で８切片を与えることになる。The in vivo absorption in vivo absorption test is carried out as follows: implanting a 2cm portion of the sample filament to hip muscle of both right and left two female rats for each period of the test. This procedure will give a total of 8 intercepts per period for periods of 5,91,119,154 and 210 days.

【００３５】移植物を指示の間隔で回収して、緩衝した
ホルマリン中で固定する。筋肉切片を調製してＨ＆Ｅで
染色し顕微鏡によって調べる。組織反応を評価し、残存
するフイラメントの直径を測定する。５日後のフイラメ
ント直径を、それ以降の期間後に残存する断面積百分率
を決定するための１００％基準点として用いる。Implants are harvested at the indicated intervals and fixed in buffered formalin. Muscle sections are prepared, stained with H & E and examined microscopically. The tissue reaction is evaluated and the diameter of the remaining filament is measured. The filament diameter after 5 days is used as the 100% reference point for determining the percentage of cross-sectional area remaining after the subsequent period.

【００３６】実施例１１パイロツトプラント規模の反応器中の９０／１０初期重
量組成(９１．１／８．９モル％)におけるポリジオキサ
ノン−溶融物／グリコリドの製造 十分に乾燥し、機械
的に撹拌した１０ガロンのステンレス鋼ヘリコーン反応
器中に、窒素パージ下に、１０．０５０g(９８．５２９
モル)のp−ジオキサノン、１０．９５ｍｌのオクタン酸
すず触媒溶液(トルエン中０．３３モル％濃度)、１５．
１３gの１ードデカノール及び１１．１６gのＤ＆Ｃバイ
オレツト＃２染料を入れた。反応器内容物を水銀中１mm
以下の真空下に２０分保った。真空を乾燥窒素で解除
し、内容物に再び少なくとも水銀柱１mmの真空をさらに
２０分間付与した。反応器を窒素でパージした。反応混
合物を１１０℃に加熱した。重合時間は反応混合物が１
００℃に達してから６時間とした。６時間の第１期重合
期間(インヘレント粘度１．２３＝ｄｌ／ｇの未反応モ
ノマー＝２２．８％)の終りに、１１１７g(９．６２９
モル)のグリコリドを窒素パージ下に反応器に加えた。
温度を約１４５℃に上げて3／4時間保った。重合物を単
離し、摩砕し、ふるいにかけたのち、１立方フイートの
真空転回乾燥機中で室温で１０時間、次いで７０℃で３
２時間乾燥し、その後に４時間の冷却時間をかけて未反
応モノマーを除去した。重合体の性質の要約を第４表中
に示す。Example 11 90/10 initial weight in a pilot plant scale reactor
Polydioxa in quantitative composition (91.1 / 8.9 mol%)
Non-Melt / Glycolide Preparation 10.050 g (98.529) under a nitrogen purge in a fully dried, mechanically stirred 10 gallon stainless steel helicone reactor.
14. mol of p-dioxanone, 10.95 ml of a tin octoate catalyst solution (0.33 mol% concentration in toluene), 15.
13 g of 1-dodecanol and 11.16 g of D & C violet # 2 dye were added. 1 mm of reactor contents in mercury
It was kept under the following vacuum for 20 minutes. The vacuum was released with dry nitrogen and the contents reapplied with a vacuum of at least 1 mm of mercury for a further 20 minutes. The reactor was purged with nitrogen. The reaction mixture was heated to 110 ° C. Polymerization time is 1 for reaction mixture
It took 6 hours after the temperature reached 00 ° C. At the end of the first polymerization period of 6 hours (inherent viscosity 1.23 = dl / g unreacted monomer = 22.8%), 1117 g (9.629)
Mol) glycolide was added to the reactor under a nitrogen purge.
It kept 3/4 hours by raising the temperature to about 145 ℃. The polymer was isolated, ground and sieved, then in a 1 cubic foot vacuum tumble dryer at room temperature for 10 hours and then at 70 ° C. for 3 hours.
After drying for 2 hours, unreacted monomer was removed by cooling for 4 hours. A summary of the polymer properties is shown in Table 4.

【００３７】第４表 インヘレント粘度 2.18ｄｌ／ｇ Ｔg(ＤＳＣ) −5℃ Ｔm(ＤＳＣ) 112℃ 結晶化度(Ｘ線) 33％ PDO/PGモル比(NMRによる) 86.3/13.7 実施例１２ 共重合体を１３０〜１６０℃で溶融し、その溶融物を５
／１の長さの直径に対する比を有する６０ミルの毛細管
中に圧入することによって、モノフイラメントとして押
出した。押出物を、水浴中に通じることによって急冷し
たのち、ロール上で２段階で延伸した。第一段の延伸は
室温のロール上で行ない、第二段の延伸は加熱オーブン
中で行なった。実施例１２の処理条件の一部を以下に示
す： ブロツク／ダイ温度(℃) 145/139 第一ゴデツト速度、(fpm) 13 全延伸比 5.4X オーブン温度(℃) 68 結晶化時間(分) 7-8 繊維を室温で終夜結晶化させたのち、加熱オーブン中で
１段で再延伸した。再延伸後に、試料を９０℃において
０％の緩和のもとで窒素下に６時間焼きなましした。 Table 4 Inherent viscosity 2.18 dl / g Tg (DSC) -5 ° C Tm (DSC) 112 ° C Crystallinity (X-ray) 33% PDO / PG molar ratio (by NMR) 86.3 / 13.7 Example 12 Co The polymer is melted at 130-160 ° C. and the melt is
It was extruded as a monofilament by pressing into a 60 mil capillary with a length to diameter ratio of 1/1. The extrudate was quenched by passing it through a water bath and then stretched on rolls in two stages. The first stage stretching was performed on a roll at room temperature, and the second stage stretching was performed in a heating oven. Some of the processing conditions for Example 12 are shown below: Block / Die Temperature (° C) 145/139 First Goddet Speed, (fpm) 13 Total Stretch Ratio 5.4X Oven Temperature (° C) 68 Crystallization Time (min) The 7-8 fiber was allowed to crystallize overnight at room temperature and then redrawn in one stage in a heated oven. After re-stretching, the samples were annealed at 90 ° C. under 0% relaxation under nitrogen for 6 hours.

【００３８】太さ２／０の実施例１２の繊維の物理的性
質を同様な寸法の市販の染色p−ジオキサノンホモポリ
マーモノフイラメント(ＰＤＯ)と比較して第５表に示
す。The physical properties of the 2/0 thickness Example 12 fibers are shown in Table 5 in comparison with a commercially available dyed p-dioxanone homopolymer monofilament (PDO) of similar size.

【００３９】 本発明の共重合体は、重合したp−ジオキサノンとグリ
コリドの共重合体鎖に共役結合した重合p−ジオキサノ
ンの長いシーケンスから成っている。共重合体のＮＭＲ
分析はコモノマーが共役結合していることを確証する。
共重合体のＸ線分析は１種以上のコモノマー種の結晶性
の存在を示す。またこれは結晶性を生じさせるために十
分に長い１モノマー種のセグメントの存在を示す。これ
らの両分析法は本発明の共重合体がランダム共重合体
(ランダム共重合体は一般に本質的に非結晶性である)で
はないという見解を支持する。ゲル浸透クロマトグラフ
イーのデータは、本発明の共重合体が一つのみの分子量
分布曲線を有しており、それ故、２種以上の異なる重合
体のブレンドではないということを示す。[0039] The copolymer of the present invention comprises a long sequence of polymerized p-dioxanone conjugated to the copolymer chain of polymerized p-dioxanone and glycolide. NMR of copolymer
The analysis confirms that the comonomers are covalently linked.
X-ray analysis of the copolymer shows the crystalline presence of one or more comonomer species. It also indicates the presence of a segment of one monomer species long enough to cause crystallinity. In both of these analysis methods, the copolymer of the present invention is a random copolymer.
We support the notion that (random copolymers are generally amorphous in nature). Gel permeation chromatography data show that the copolymers of the invention have only one molecular weight distribution curve and therefore are not blends of two or more different polymers.

【００４０】本発明の共重合体から製造した延伸し且つ
配向したフイラメントは、高い含量の重合したグリコリ
ドを有する重合体から成るフイラメントの生体内吸収特
性(本発明の共重合体は比較的僅かな割合の重合したグ
リコリドを含有するに過ぎないのにかかわらず)を表わ
す。しかしながら、本発明のフイラメントは高グリコリ
ド含量の重合体から成るフイラメントよりも遥かに柔軟
性である。それ故、本発明のフイラメントはモノフイラ
メント形態で手術用縫合糸及び結紮具として用いること
ができる:それらは編組する必要がない。この特色を例
証するものとして、グリコリドホモポリマー又は９０／
１０グリコリド／ラクチド共重合体から成るフイラメン
トは、一般に２×１０6の程度のヤング率値を有してい
るのに対して、本発明の好適重合体から延伸配向したフ
イラメントは、１桁低い、約３×１０5以下のヤング率
値を有している。Stretched and oriented filaments made from the copolymers of the invention are bioabsorbable properties of filaments composed of polymers having a high content of polymerized glycolide. (Although it only contains a proportion of polymerized glycolide). However, the filaments of the present invention are much more flexible than filaments composed of high glycolide content polymers. Therefore, the filaments of the present invention can be used as surgical sutures and ligatures in monofilament form: they do not need to be braided. As an illustration of this feature, glycolide homopolymer or 90 /
Whereas filaments composed of 10 glycolide / lactide copolymers generally have Young's modulus values on the order of 2 × 10 6 , filaments stretch oriented from the preferred polymers of the invention are an order of magnitude lower, It has a Young's modulus value of about 3 × 10 5 or less.

【００４１】比較として、緩和なしに、６０℃で１２時
間焼きなましした、実施例９及び１０の共重合体から製
造した、サイズ４／０モノフイラメントの生体内ＢＳＲ
を、第６表中で、サイズ４／０の編組した９０／１０グ
リコリド／ラクチド共重合体の生体内ＢＳＲと比較す
る。For comparison, in vivo BSR of size 4/0 monofilament, prepared from the copolymers of Examples 9 and 10, annealed at 60 ° C. for 12 hours without relaxation.
In Table 6 with in vivo BSR of a braided 90/10 glycolide / lactide copolymer of size 4/0.

【００４２】 第６表 実施例9 実施例10 90/10PG/PL* 編 組 ベースライン、 ポンド 4.2 4.0 5.5 ＢＳＲ％,３週 28 30 29 ＢＳＲ％,４週 17 12 5 ＊典型値 本発明の共重合体は以下のように特徴付けることができ
る：７５〜９７重量パーセントの重合したp−ジオキサ
ノンを含有し、残部は重合したグリコリドである。好適
な手術用フイラメントとしての使用のためには、共重合
体は約９０〜９７モルパーセントの重合したp−ジオキ
サノンを含有し、残部は重合したグリコリドである。[0042] Table 6 Example 9 Example 10 90 / 10PG / PL * knitted sets baseline lbs 4.2 4.0 5.5 BSR%, 3 weeks 28 30 29 BSR%, 4 weeks 17 12 5 * typical value co of the present invention The polymer can be characterized as follows: It contains 75 to 97 weight percent polymerized p-dioxanone, the balance being polymerized glycolide. For use as the preferred surgical filament, the copolymer contains about 90 to 97 mole percent polymerized p-dioxanone, the balance being polymerized glycolide.

【００４３】自然(未染色)状態において、共重合体は熱
載物台顕微鏡法による約９０〜１２５℃の融点を有して
いる(染料の添加は５℃程度の融点の上昇を生じさせる
ものと思われる)。In its natural (undyed) state, the copolymer has a melting point of about 90 to 125 ° C. according to thermal stage microscopy (addition of a dye causes an increase in melting point of about 5 ° C.). I think that the).

【００４４】溶融状態において、共重合体は光学顕微鏡
による観察により単一相を有している。In the molten state, the copolymer has a single phase as observed by an optical microscope.

【００４５】Ｘ線回折分析により、共重合体は約２５〜
５０％の結晶化度を有している。According to X-ray diffraction analysis, the copolymer is about 25 to
It has a crystallinity of 50%.

【００４６】ゲル浸透クロマトグラフイーによって、本
発明の共重合体は単一の分子量分布曲線を示すのみであ
る;インヘレント粘度値は１．６〜２．６ｄｌ／ｇであ
る。By gel permeation chromatography, the copolymers of the present invention show only a single molecular weight distribution curve; the inherent viscosity values are 1.6 to 2.6 dl / g.

【００４７】本発明の共重合体から製造したモノフイラ
メントの性質は、ＰＤＯ／ＰＧモル比、共重合条件、延
伸と焼きなましの条件、分子量、及びフイラメントの太
さを包含する多くの要因に依存する。一般に、好適重合
体(これは９０／１０乃至９７／３のＰＤＯ／ＰＧモル
比を有する)から製造した延伸し且つ焼きなまししたフ
イラメントは、下記の性質を有している: 引張強さ、ＫＳＰＩ 70-120 結節強さ、ＫＳＰＩ 40-80 伸び、％ 25-60 ヤング率、ＫＳＰＩ 150-300 生体内ＢＳＲ、％ ３週 20-50％ ４週 10-30％ 生体内吸収、ゼロまで 4〜5ケ月未満The properties of monofilaments prepared from the copolymers of the present invention depend on many factors, including the PDO / PG molar ratio, the copolymerization conditions, the stretching and annealing conditions, the molecular weight, and the thickness of the filaments. . In general, drawn and annealed filaments made from the preferred polymer, which has a PDO / PG molar ratio of 90/10 to 97/3, have the following properties: Tensile Strength, KSPI 70 -120 Knot strength, KSPI 40-80 elongation,% 25-60 Young's modulus, KSPI 150-300 In vivo BSR,% 3 weeks 20-50% 4 weeks 10-30% In vivo absorption, 4 to 5 months to zero Less than

───────────────────────────────────────────────────── フロントページの続き (72)発明者 シヤラビイ・ウオーバ・シヤラビイ アメリカ合衆国ニユージヤージイ州08833 レバノン・アールデイ２・ロングビユーロ ード328エイ (72)発明者 ヒユー・デイ・ニユーマン・ジユニア アメリカ合衆国ニユージヤージイ州07930 チエスター・ラーチドライブ（番地なし) ─────────────────────────────────────────────────── ───Continued from the front page (72) Inventor Syaraby Uover Syaraby United States New Jersey 08833 Lebanon Earlday 2 Longview Road 328 rays (72) Inventor Hiyu Day Newman Junia United States New Jersey 07930 Cheester Larch drive (no address)

Claims (2)

【特許請求の範囲】[Claims] 【請求項１】 約３乃至約３０重量パーセントの重合し
たグリコリドを含有し、残りが重合したp−ジオキサノ
ンであり、且つ１.６〜２.６ｄｌ／ｇのインヘレント粘
度；加熱載物台顕微鏡測定によって９０〜１２５℃の溶
融温度；２５〜５０％の結晶化度；単一の分子量分布曲
線；及び溶融状態における単一相を有することを特徴と
するp−ジオキサノンとグリコリドの結晶性共重合体。1. A polymer containing about 3 to about 30 weight percent polymerized glycolide, the remainder being polymerized p-dioxanone, and an inherent viscosity of 1.6 to 2.6 dl / g; Crystalline copolymer of p-dioxanone and glycolide characterized by having a melting temperature of 90-125 ° C .; a crystallinity of 25-50%; a single molecular weight distribution curve; and a single phase in the molten state. . 【請求項２】 ９０〜９７モルパーセントの重合したp
−ジオキサノンを含有し、残りが重合したグリコリドで
ある請求項１に記載の結晶性共重合体。2. 90-97 mole percent polymerized p
-The crystalline copolymer according to claim 1, which contains dioxanone and the rest is polymerized glycolide.
JP8035707A 1985-11-29 1996-01-31 Crystalline copolymer of p-dioxanone and glycolide Expired - Lifetime JP2713397B2 (en)

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US4653497A (en) 1987-03-31
DE3640658C2 (en) 1999-12-02
JP2713397B2 (en) 1998-02-16
JPH08259685A (en) 1996-10-08
JPS62164726A (en) 1987-07-21
JP2537500B2 (en) 1996-09-25
JP2788219B2 (en) 1998-08-20
DE3640658A1 (en) 1987-06-04

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